AbstractIsolation of a monomeric SiO2 compound 3 as a stable donor–acceptor complex with two different ligands —a σ‐donating ligand (pyridine, dimethylaminopyridine, N‐heterocyclic carbene) and a donor–acceptor ligand (iminophosphorane)—is presented. The SiO2 complex 3 is soluble in ordinary organic solvents and is stable at room temperature in solution and in the solid state. Of particular interest, 3 remains reactive and can be used as a stable and soluble unimolecular SiO2 reagent.